Fiber-reactive triphenodioxazine dyes

ABSTRACT

PCT No. PCT/US94/03233 Sec. 371 Date Jul. 11, 1995 Sec. 102(e) Date Jul. 11, 1995 PCT Filed Mar. 24, 1994 PCT Pub. No. WO94/21646 PCT Pub. Date Sep. 29, 1994The invention is that of a new triphenodioxazine dye of the formula:   &lt;IMAGE&gt;   wherein:   &lt;IMAGE&gt;    &lt;IMAGE&gt;   K is independently selected from SO3H and COOH; W=a substituted or unsubstituted arylene, alkylene or arylene-alkylene group; Y1=Vinyl,  beta -Sulfatoethyl,  beta -Thiosulfatoethyl,  beta -Halogenethyl-group,  beta -Phosphatoethyl, and X=H. R, R1 and R2 are independently selected from hydrogen and substituted or unsubstituted alkyl. T is independently selected from hydrogen, Cl, Br, C1 to C6 alkyl, C1 to C6 alkoxy, phenyl or phenoxy; and n is selected from 0, 1 or 2.

CROSS REFERENCES TO RELATED APPLICATIONS

This is a 35USC371 national stage application of PCT/US94/03233, filedMar. 24, 1994, and is a continuation-in-part of U.S. patent applicationSer. No. 08/036,611 filed Mar. 24, 1993 now; abandoned.

BACKGROUND OF THE INVENTION

1. Technical Field

This invention is directed to new fiber reactive triphenodioxazine dye.

2. Background

Anthraquinone based fiber reactive dyes have been the predominate dyeused in the coloring of cotton fabdcs in bright blue colors. Thisdominance of the anthraquinone dyes has been threatened over the pastdecade or so by the increasing use of dyes based upon thetriphenodioxazine chromophore.

Examples of the recent patent activity in this triphenodioxazine baseddyes are: U.S. Pat. No. 4,604,459; U.S. Pat. No. 3,996,221; U.S. Pat.No. 4,092,478; U.S. Pat. No. 4,400,504; U.S. Pat. No. 4,472,575; U.S.Pat. No. 4,774,333; U.S. Pat. No. 4,629,788; and EPO 385,120 (Sep. 9,1990).

The present invention provides new dioxazine based fiber reactive dyeswith good fastness properties (light, chlorine and wash fastness), highsubstantivity for cellulosic fibers, high tinctorial strength and abright reddish blue color. In addition, the dyes of the invention areeasily synthesized from readily available intermediates at low costs.

SUMMARY OF THE INVENTION

The invention is that of a new triphenodioxazine dye of the formula:##STR3## wherein: ##STR4## W=a substituted or unsubstituted arylene,alkylene or arylene-alkylene group where the alkylene moiety may beinterrupted by a hetero atom selected from O, S and N;

Y¹ =Vinyl, β-Sulfatoethyl, β-Thiosulfatoethyl, β-Halogenethyl,β-Phosphatoethyl, and

X=H.

K is independently selected from SO₃ H and COOH.

R, R₁ and R₂ are independently selected from hydrogen and substituted orunsubstituted alkyl of 1 to 6 carbons; preferably hydrogen and asubstituted or unsubstituted C₁ to C₄ alkyl.

R₂ may also be selected from the group W--SO₂ --Y¹.

T is independently selected from hydrogen, Cl, Br, C₁ to C₆ alkyl, C₁ toC₆ alkoxy, phenyl or phenoxy; and

n is selected from 0, 1 or 2.

The dyes of the above formula provide dyeing on cotton substrates havinga bright reddish blue color having good fastness or properties of hightinctodal strength. The dyes of the invention may also be used in thedyeing of other textiles containing amido and/or hydroxyl groups;exemplary materials include regenerated cellulose, synthetic polyamides,wool, silk and polyurethane fibers. The dyes of the invention may beapplied by the standard methods for printing and dyeing textiles withfiber reactive dyes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention relates to new triphendioxazine reactive dyestuffs of theformula: ##STR5## wherein:

R and R₁ are independently selected from H or a substituted orunsubstituted alkyl, preferably hydrogen or a substituted orunsubstituted C₁ -C₆ - alkyl, and most preferably hydrogen or asubstituted or unsubstituted C₁ -C₄ alkyl;

T is independently selected from H, Cl, Br, a substituted orunsubstituted C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, or phenoxy;##STR6## R₂ iS selected from hydrogen or a substituted or unsubstitutedC₁ to C₆ alkyl or the group W--SO₂ --Y¹ ; preferably hydrogen or asubstituted or unsubstituted C₁ to C₄ alkyl.

W is a substituted or unsubstituted arylene, or alkylene, orarylene-alkylene group wherein the alkylene group may be interrupted bya hetero atom selected from O, S and N, preferably a substituted orunsubstituted phenylene or naphthalene group or a substituted orunsubstituted C₁ to C₆ alkylene group, wherein said alkylene moiety maybe interrupted by a hetero atom selected from O, N and S; Y¹ =Vinyl,β-Sulfatoethyl, β-Thiosulfatoethyl, β-Halogenethyl, β-Phosphato, andX=H. K is independently selected from SO₃ H and COOH. n=0, 1 or 2.

The term "arylene-alkylene" group as used in this specification and theclaims is intended to mean a phenylene or naphthalene group bonded toone or more alkylene groups, e.g. the following illustrations or theirisomers: ##STR7##

Examples of R, R₁ and R₂ are: hydrogen or CH₃, C₂ H₅, n-C₃ -H₇, n-C₄ H₉,n-C₆ H₁₃, which may be optionally substituted by OH, OCH₃, OC₂ H₅, COOH,SO₃ H, OSO₃ H, CN, Cl, or F.

Examples of the substituents in substituted C₁ -C₄ -alkyl and C₁ -C₄-alkoxy, groups are OH, OCH₃, OC₂ H₅, COOH, SO₃ H, OSO23H, CN, Cl, Br orF; preferably OCH₃, OC₂ H₅ and OSO₃ H.

Examples of the substituents in a substituted phenyl and phenoxy groupsare Cl, Br, CH₃, C₂ H₅, OCH₃, SO₃ H, COOH and OC₂ H₅.

Preferably R and R₁ are hydrogen; R₂ is preferably hydrogen, CH₃ or C₂H₅ ; W is preferably phenylene or naphthalene which may be substitutedby methyl, methoxy, carboxy and sulfo. Y¹ is preferably vinyl orsulfatoethyl, X is preferably hydrogen and n is preferably 1.

Exemplary type "Q" groups are:

2-(β-Sulfatoethylsulfonyl)-phenyl-amino,3-(β-Sulfatoethylsulfonyl)-phenyl-amino,4-(β-Sulfatoethylsulfonyl)-phenyl-amino,2-Carboxy-5-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Chloro-3-(β-Sulfatoethylsuifonyl)-phenyl-amino,2-Chloro-4-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Ethoxy-4- or5-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Ethyl-4-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Methoxy-5-(β-sulfatoethylsulfonyl)-phenyl-amino,2,3-Dimethoxy-5-(β-sulfatoethylsulfonyl)-phenyl-amino,2,4-Dimethoxy-5-(β-sulfatoethylsulfonyl)-phenyl-amino,2,5-Dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl-amino, 2or 3- or4-(β-Thiosulfatoethylsulfonyl)-phenyl-amino,2-Methoxy-5-thiosulfatoethylsulfonyl)-phenyl-amino,2-Sulfo-4-(β-phosphatoethylsulfonyl)-phenyl-amino,2-Sulfo-4-vinylsulfonyl-phenyl-amino, 2-Hydroxy-4-or-5-(β-sulfatoethylsulfonyl)-phenyl-amino,2-Chloro-4-or-5-β-chloroethylsulfonyl)-phenyl-amino,2-Hydroxy-3-sulfo-5-(β-sulfatoethylsulfonyl)-phenyl-amino, 3- or4-(β-Acetoxyethylsu lfonyl)-phenyl-amino,2-Methoxy-4-[β-(N-methyl-tauryl)ethylsulfonyl]-phenyl-amino5-(β-Sulfatoethylsulfonyl)naphth-2-yl-amino, 6- or 7- or8-(β-Sulfatoethylsulfonyl)-naphthy-2-yl-amino,6-(β-Sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl-amino,5-(β-Sulfatoethylsulfonyl)-l-sulfo-naphth-2-yl-amino,8-(β-Sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl-amino,β-[4-(β'-Sulfatoethylsulfonyl)-phen]-ethylamino,β-[-2-Sulfo-4-(β'-sulfatoethylsulfonyl)phen]ethylamino,β-(β'-Chloroethylsulfonyl)-ethylamino, β-(β'-Sulfatoethylsulfonyl)-ethylamino, β-(Vinyisulfonyl)-ethylamino,(β'-Chloroethylsulfonyl)-propylamino,γ-(β'-Sulfatoethylsulfonyl)-propylamino,γ-(β'-Bromoethylsulfonyl)-propylamino, γ-(Vinylsulfonyl)-propylamino,1-Methyl-1-(β-sulfatoethylsulfonyl)-1-ethylamino,δ-(β'-Sulfatoethylsulfonyl)-butylamino, 2-Methyl-2-(β-chloroethylsulfonyl)-1-propylamino,ω-(β'-Chloroethylsulfonyl)-pentylamino,β-(β'-Chloroethylsulfonyl)-n-hexyalmino,N-Methyl-N-[β-(β'chloroethylsulfonyl)-ethyl]-amino,N-Ethyl-N-[β-(β'-chloroethyisulfonyl)ethyl]-amino,N-n-Propyl-N-[β-(β'chloroethylsulfonyl)-ethyl]-amino,N-Carboxymethyl-N-[β-(β'-bromoethylsulfonly)-ethyl]-amino,N-Sulfatomethyl-N-[β-(β'-chloroethylsulfonyl)-ethyl]-amino,N-(β-Carboxyethyl)-N-[-γ'-(β-chloroethylsulfonyl)-propyl-amino-N-(β-Sulfatoethyl)-N-[γ-(β"chloroethylsulfonyl)-propyl-amino-N-(β-(βSulfatoethyl)-N-[,δ'(β"chloroethylsulfonyl)-butyl]-amino,N-(β-Ethoxyethyl)-N-[δ'-(β"-chloroethylsulfonyl)-butyl]-amino,N-(γ-Chloropropyl)-N-[δ'(β"-chloroethylsulfonyl)-butyl]-amino,N-Phenyl-N-[β-(β'-chloroethylsulfonyl)-ethyl]-amino,N-(3-Sulfophenyl)-N-[β-(β'-chloroethylsulfonyl)-ethyl]amino,N-(4-Sulfophenyl)-N-[β-(β'-chloroethylsulfonyl)-ethyl]-amino,

Bis-[β-(β'-chloroethylsulfonyl)-ethyl]-amino,

Bis-[β-(β'-bromoethylsulfonyl)-ethyl]-amino,

Bis-[γ-(β'-chloroethylsulfonyl)-propyl]-amino,

Bis-[δ-(β'-chloroethyisulfonyl)-butyl]-amino,

Bis-(β-vinylsulfonyl-ethyl)-amino,N-(β-Cyanoethyl)-N-[γ'-β"-chloroethylsulfonyl)-propyl]-amino,

β[β'-(β"-Chloroethylsulfonyl)-ethylamino]-ethylamino,

β[β'(β"- Sulfatoethylsulfonyl)-ethylamino]-ethylamino,

β-[β'(β"-Chioroethylsuifonyl)-ethoxy]-ethylamino,

β-β'-β"-Sulfatoethylsulfonyl)-ethoxy]-ethylamino,

3,4-Di-(β-sulfatoethylsulfonyl)-phenylamino,

2,5-Di(β-sulfatoethylsulfonyl)-phenylamino,

4-[γ-(β'Sulfatoethylsulfonyl)-propoxy]-phenylamino,

2,5-Bis-[(β-sulfatoethylsulfonyl)-methyl], phenylamino,

N-Methyl-N-[4-(β-sulfatoethylsulfonyl)-phenyl]-amino,

N-Methyl-N-[3-(β-sulfatoethylsulfonyl)-phenyl]-amino,

N-Ethyl-N-[4-(β-sulfatoethylsulfonyl)-phenyl]-amino,

N-Ethyl-N-[3-(β-sulfatoethylsulfonyl)-phenyl]-amino, and halogen(chloro, fluoro and bromo).

Dyestuffs which are preferred having the following general Formula 1A:##STR8## wherein T₁, R, R₁ and Q have the above mentioned meaning.

The moiety Q may be represented by the formula: ##STR9## wherein D isindependently selected from a covalent bond or a C₁ to C₆ alkylene groupwhich may be optionally interrupted by a hetero atom selected from O, Nand S; Y¹ is defined above, and R₄ is selected from H, Cl, Br, C₁ to C₄alkyl, C₁ to C₄ alkoxy or phenoxy and R₂ is as previously defined.

Preferred dyestuffs of Formula 1 are those in which ##STR10## where thebenzene ring A can contain further substituents. Examples of suchsubstituents are: CH₃, C₂ H₅, OCH₃, OC₂ H₅, Cl, COOH, and SO₃ H.

The invention also relates to a process for preparing the dyestuffs ofthe Formula 1 wherein X is hydrogen. This process is characterized inthat about 1 mole of a triphenodioxazine dyestuff of the Formula 2.##STR11## preferably in the form of the corresponding lithium salts iscondensed with about 1 to 1.3 moles of 2,4,6-trichlorotriazine withelimination of 1 mole hydrochloric acid, preferably using basic lithiumcompounds such as lithium hydroxide or lithium carbonate as acidacceptors, to give the triphenodioxazine/dichlorotriazine condensationproduct, which then is reacted with about 1 mole of cyanamide of theFormula 3:

    H.sub.2 N--CN                                              (Formula 3)

with the elimination of 1 mole of hydrochloric acid. The resultingmonochloromonocyanamido compound is then reacted with about 1 mole of anamine of the Formula 4:

    H--Q                                                       (Formula 4)

with the elimination of 1 mole hydrochloric acid to give the dyestuff ofFormula 1. In both the last steps, basic alkali such as lithiumhydroxide, lithium carbonate, sodium hydroxide and sodium carbonate canbe used as acid acceptors.

An alternative to the above described process is the reaction of about 1mole of 2,4,6-trichloro-triazine with 1 mole of cyanamide of the Formula3, to the dichloro-monocyanamido compound of the Formula 5. ##STR12##

This compound is then reacted with about 1 mole of amine of the Formula4 to give a compound of Formula 6. ##STR13##

This compound is then reacted with about 1 mole of triphenodioxazinedyestuff of the Formula 2 to give the dye of Formula 1. In all stepshydrochloric acid is eliminated, which is neutralized by using a basicalkali compounds such as lithium hydroxide, lithium carbonate, sodiumhydroxide and sodium carbonate.

An other alternative for preparing the dyestuffs of the Formula 1 isfirst reaction of 1 mole o 2,4,6-trichlorotdazine with 1 mole ofcyanamide of the Formula 1 to the dichloromonocyanamido compound ofFormula 5. This compound is then reacted with 1 mole of thetriphenodioxazine dyestuff of the Formula 2 to give themonochloro-monocyanamido-triphendioxazine-triazine compound of Formula7. ##STR14##

Finally the compound of Formula 7 is reacted with approximately 1 moleof an amine of the Formula 4. In all steps hydrochloric acid iseliminated, which is accepted by using basic alkali compounds such aslithium hydroxide, lithium carbonate, sodium hydroxide and sodiumcarbonate.

Examples of the H--Q amines are the amines of the above mentioned amineradicals Q.

The preparation of compounds of the Formula 2 is effected by methodsknown to those skilled in the art by condensing 1,4-benzoquinones of theformula: ##STR15## wherein

T has the above mentioned meaning and R₃ is independently selected fromH, Cl, Br, a substituted or unsubstituted alkyl, a substituted orunsubstituted alkoxy or phenoxy, with diaminobenzenes of the formula:##STR16## wherein R, R₁, and no have the above mentioned meaning, togive a compound of the formula: ##STR17## and subsequently cyclizing thediaminobenzene or dianilino compound 10 to give the basic dioxazinedyestuff of Formula 2.

The benzoquinones of Formula 8 are best condensed with thediaminobenzenes of the Formula 9 at temperatures of 0°-70° C.,preferably 20°-50° C., and at pH 2-10, preferably pH 5-7, in an aqueousor aqueous-organic medium in the presence of alkaline condensing agents.It is also possible to work in a purely organic medium in the presenceof acid-binding agents. The condensation products of the Formula 10 canbe precipitated by salting out or by acidification.

Examples of suitable organic mediums are methanol, ethanol, andnitrobenzene. Examples of suitable acid-binding agents are sodiumbicarbonate, sodium carbonate, sodium acetate, potassium acetate, sodiumhydroxide, potassium hydroxide, sodium phosphates and sodium borate.

Examples of suitable diaminobenzenes of the Formula 8 are as follows:1,4-Diaminobenzene-2-sulfonic acid, 1,4-Diaminobenzene-2-carboxy acid, 1-Amino-4-N-methylaminobenzene-3-sulfonic acid,1-Amino-4-N-ethylaminobenzene-3-sulfonic acid,1,4-Diamono-2-methoxybenzene-5-sulfonic acid,1,4-Diamono-2-methylbenzene-5-sulfonic acid,1,4-Diaminobenzene-2,5-disulfonic acid, 1,4-Diaminobenzene-2,5-dicarboxyacid, 1,4-Diamino-2-carboxybenzene-5-sulfonic acid.

The cyclization of the dianilino compounds of the Formula 10 can beeffected by methods known to those skilled in the art; see e.g., U.S.Pat. No. 4,604,459 and A.H.M. Renfrew, J.Soc. Dyers Colour, 105 (1989)262-4, GB Patent No. 1,589,915 in particular, at temperatures of 10°-80°C. in oleum having SO₃ contents of 1-50%, in the absence of presence ofoxidizing agents such as potassium peroxodisulphate, ammoniumperoxodisulphate or organic peroxides.

In general, oleum having an SO₃ content of 5-30% is used in an amount ofabout 5-15 parts by weight per part by weight of the compound of Formula10.

Under the reactive conditions for cyclization in oleum it is possible tosulfonate aliphatic OH groups and sulfonate aromatic rings present inthe dianilino compounds of the Formula 10; therefore milder conditionsmust be used if undesired sulfonation is encountered.

The new dyestuffs produce bright reddish blue dyeings on cellulose andnatural or synthetic polyamide materials. They are distinguished by hightinctorial strength. As water-soluble reactive dyestuffs, the newdyestuffs are preferably of interest for the dyeing of hydroxyl- andamido-containing textile materials, in particular materials in naturaland regenerated cellulose and synthetic polyamide and polyurethanefibers, wool and silk.

These materials may be dyed or pdnted using the methods which arecommonly known and customary in industry for water-soluble reactivedyestuffs. The dyeing are then light- and wet-fast blue dyeings andprints.

The temperatures in the Examples are given in °C. The formulae ofwater-soluble reactive dyestuffs in the description and in the Examplesare shown in the free acid form. In general, the dyestuffs are isolatedand used in the form of their alkali metal salts, in particular in theform of the lithium, sodium or potassium salts. The preferred form ofthe fiber-reactive moiety Y¹ is the β-sulfatoethylsulfonyl group and theformula that follow show Y¹ in that form. It will be readily apparent tothose skilled in the art that equivalent vinyl, phosphato thiosulfatoetc. group may be used. It will also be apparent to the skilled workerthat the reaction mixture may be a mixture of fiber reactive moietiesand depending on the reaction conditions e.g. up to 30% of the vinylmoiety and up to about 5% of the non-reactive hydroxy moiety may beformed.

EXAMPLE 1

21.8 parts of 2,9-diamino-6,13-dichlorotriphenodioxazine- 1,8-disulfonicacid is suspended in 1000 parts of water and brought to pH 7.0 by usingan aqueous solution of 5% LiOH. The reaction mixture is stirred for onehour until complete solution. The pH is adjusted with hydrochloric acidto 4.5 and 7.8 parts of 2,4,6-tdchlorotriazine is added. The reactionmixture is stirred for 3 hours at room temperature and the pH maintainedat 4.5 using an aqueous solution of 5% LiOH. To the resulting pdmarycondensation product 2.5 parts of cyanamide in form of a 50% aqueoussolution is added and the pH adjusted to 9.0 using LiOH. The reactionmixture is heated up to 45° -40° C. for 3 hours by maintaining the pH.After adjusting the pH to 4.0 of the resulting secondary condensationproduct, 14.0 pans of 1-amino-3-[βsulfatoethylsulfonyl]-benzene isadded. After stirring for 6 hours at 80° C. at pH 5.5 the reaction iscompleted. High performance liquid chromatography can be used in allsteps to indicate the end of each condensation. The resulting dyestuffsolution is clarified and spray dried. It results in a blue dyestuffpowder, which, if applied to cotton in one of the methods customary forreactive dyestuffs, produces brilliant strongly reddish bluish shades.

The dyestuff in form of the free acid has the following formula:

    (λmax: 574 nm) ##STR18##

EXAMPLE 2

21.8 pans of 2,9-diamino-6,13-dichlorotriphenodioxazine- 1,8-disulfonicacid is suspended in 1000 pans of water and brought to pH 7.0 by usingan aqueous solution of 5% LiOH. The reamion mixture is stirred for onehour until complete solution. The pH is adjusted with hydrochloric acidto 4.5 and 7.8 pans of 2,4,6-trichlorotriazine is added. The reactionmixture is stirred for 3 hours at room temperature and the pH maintainedat 4.5 using an aqueous solution of 5% LiOH. The resulting primarycondensation product 2.5 parts of cyanamide in form of a 50% aqueoussolution is added and the pH adjusted to 9.0 using LiOH. The reamionmixture is heated up to 45° -40° C. for 3 hours by maintaining the pH.After adjusting the pH to 4.0 of the resulting secondary condensationproduct, 14.0 parts of1-amino-3-[β-sulfatoethyl-sulfonyl]-5-methoxy-benzene is added. Afterstirring for 6 hours at 80° C. at pH 5.5 the reaction is completed. Highperformance liquid chromatography can be used in all steps to indicatethe end of each condensation. The resulting dyestuff solution isclarified and spray dried. It results in a blue dyestuff powder, which,if applied to cotton in one of the methods customary for reactivedyestuffs, product brilliant strongly reddish bluish shades. Thedyestuff in form of the free acid has the following formula:

    (λmax: 575 nm) ##STR19##

Additional dyestuffs of the following general Formula A. These compoundshades dye cotton in bright, strong, reddish blue shades are obtained byusing the procedure of the above examples. ##STR20## Examples 3-31illustrate compounds of the general Formula A wherein the substituents Tand Q are as follows:

EXAMPLES 3-31

    __________________________________________________________________________    Ex.                                                                              T  Q                                                                       __________________________________________________________________________     3 Cl                                                                                ##STR21##                                                               4 Cl                                                                                ##STR22##                                                               5 Cl                                                                                ##STR23##                                                               6 Cl                                                                                ##STR24##                                                               7 Cl                                                                                ##STR25##                                                               8 Cl                                                                                ##STR26##                                                               9 Cl                                                                                ##STR27##                                                              10 Cl                                                                                ##STR28##                                                              11 Cl                                                                                ##STR29##                                                              12 Cl                                                                                ##STR30##                                                              13 Cl                                                                                ##STR31##                                                              14 Br                                                                                ##STR32##                                                              Ex.                                                                              Q  T                                                                       __________________________________________________________________________    15 Br                                                                                ##STR33##                                                              16 Br                                                                                ##STR34##                                                              17 Br                                                                                ##STR35##                                                              18 Br                                                                                ##STR36##                                                              19 Br                                                                                ##STR37##                                                              20 Cl                                                                                ##STR38##                                                              21 Cl N(CH.sub.2CH.sub.2SO.sub.2CHCH.sub.2).sub.2                             22 Cl                                                                                ##STR39##                                                              23 Cl                                                                                ##STR40##                                                              24 Cl                                                                                ##STR41##                                                              25 Cl                                                                                ##STR42##                                                              26 Cl                                                                                ##STR43##                                                              27 Br                                                                                ##STR44##                                                              28 Cl                                                                                ##STR45##                                                              29 Br                                                                                ##STR46##                                                              30 Cl N[CH.sub.2CH.sub.2CH.sub.2SO.sub.2CH.sub.2CH.sub.2Cl].sub.2             31 Cl N[CH.sub.2CH.sub.2CH.sub.2SO.sub.2CHCH.sub.2 ].sub.2                    __________________________________________________________________________

EXAMPLE 32

To 6.5 parts of 2,4,6-trichlorotriazine in 50 parts of water and 50parts of ice, 1.5 parts of cyanamide in form of a 50% aqueous solutionis added. The reaction mixture is stirred for 1.5 hours at 0°-3° C. atpH 8.5-9.5. After adjusting the pH to 7.0 of the resulting primarycondensation product, a suspension of 10.1 parts 1-amino-4-[β-sulfatoethylsulfonyl]-benzene in 40 parts of water, whichwas adjusted to pH 4.5 using soda ash, is added. The mixture is stirredfor 5 hours at 5°-8° C. while the pH is dropping to 1.5. The pH of thesolution of the resulting secondary condensation product is adjusted to5.5 with soda ash and clarified. This solution is then added over 4hours to a solution of 13.7 parts of 2,9-diamino-6,13-dichlorotriphenodioxazine-1,8-disulfonic acid, which was brought topH 5.0 using aqueous 5% LiOH. During the addition, the temperature iskept at 80°-85° C. and the pH at 3.0-3.5. The end of each condensationstep can be monitored by using the high pedormance liquidchromatography. The resulting dyestuff solution is salted out with 15%by volume of sodium chloride. After drying and grinding it results in ablue dyestuff powder, which, if applied to cotton in one of the methodscustomary for reactive dyestuffs, produces brilliant strongly reddishbluish shades.

The dyestuff in form of the free acid has the following formula:

    (λmax: 588 nm) ##STR47##

Further similar reddish blue dyestuffs can be obtained by replacing the1,4-Diaminobenzene-3-sulfonic acid by 1,4-Diamino-benzene-3-carboxy acidduring the chromophore synthesis, and using the procedure of the abovesamples. These compounds have the following general Formula B: ##STR48##

Examples 33-44 illustrate compounds of the general Formula B wherein thesubstituents T and Q are as follows:

EXAMPLE 33-44

    ______________________________________                                        Ex.   T      Q                                                                ______________________________________                                        33    Cl                                                                                    ##STR49##                                                       34    Cl                                                                                    ##STR50##                                                       35    Cl                                                                                    ##STR51##                                                       36    Cl                                                                                    ##STR52##                                                       37    Br                                                                                    ##STR53##                                                       38    Br                                                                                    ##STR54##                                                       39    Cl                                                                                    ##STR55##                                                       40    Cl                                                                                    ##STR56##                                                       41    Cl                                                                                    ##STR57##                                                       42    Cl                                                                                    ##STR58##                                                       43    Cl     Cl                                                               44    Br     Cl                                                               ______________________________________                                    

EXAMPLE 45

21.8 parts of 2,9-diamino-6,13-dichlorotriphenodioxazine-1,8-disulfonicacid is suspended in 1000 parts of water and brought to pH 7.0 by usingan aqueous solution of 5% LiOH. The reaction mixture is stirred for onehour until complete solution. The pH is adjusted with hydrochloric acidto 4.5 and 7.8 parts of 2,4,6-tdchlorotriazine is added. The reactionmixture is stirred for 3 hours at room temperature and the pH maintainedat 4.5 using an aqueous solution of 5% LiOH. To the resulting pdmarycondensation product 2.5 parts of cyanamide in form of a 50% aqueoussolution is added and the pH adjusted to 9.0 using LiOH. The reactionmixture is heated up to 45°-40° C. by maintaining the pH. After stirringfor 3 hours the reaction is completed. High performance liquidchromatography can be used in all steps to indicate the end of eachcondensation. The resulting dyestuff solution is spray dried. IT resultsin a blue powder, which, if applied to cotton in one of the methodscustomary for reactive dyestuffs, produces brilliant strongly reddishbluish shades.

The dyestuff in form of the free acid has the following formula:

    (λmax: 582 nm ) ##STR59##

The above procedure can be used to produce other dyes having thefollowing general Formula C: ##STR60##

The above procedure used to prepare a dye in the substituent Q and T areas follows:

EXAMPLE 46

    ______________________________________                                        Ex.              T     Q                                                      ______________________________________                                        46               Cl    Cl                                                     ______________________________________                                    

Dyes prepared according to the present invention are suitable for thedyeing of cellulosic materials such as cotton, linen, viscose, rayon orstaple fibers. They can be applied by any one of the usual dyeing andprinting methods for reactive dyestuffs and yield on cellulosicmaterials, in the presence of alkaline agents, brilliant shades havingexcellent fastness properties, and high color yield and reduced coldwater bleeding. These dyes may also be used on wool, silk or polyamidefibers.

The dyes of the present invention exhibit an unexpected and highlyadvantageous property in that they can be used at very low saltconcentration in the dye bath while at the same time providing excellentdyeing yield. In the exhaust dyeing method using fiber reactive vinylsulfone type dyes, one necessary auxiliary chemical is an electrolytewhich is added to the dye bath to force the dye to migrate from solutionto the fiber. The most commonly used electrolyte is an inorganic saltsuch as sodium sulfate or sodium chloride. In exhaust dyeing procedures,this electrolyte is generally employed in amounts from about 20-50 gramsper liter to about 100 grams per liter of dye bath with the amount ofelectrolyte being proportionally higher as the amount of dye employed inthe dyeing increases. A few fiber reactive dyes are known which can beused at reduced electrolyte concentration. However, some loss in dyeyield occurs even with these dyes as the salt concentration is decreasedin the dye bath. Surprisingly the dyes of this invention achieve optimumdye yield at a very low salt concentration. After the dyeing process iscompleted, the exhausted dye bath solution is discharged to waste watertreatment facilities for removal of electrolyte and other residual dyebath chemicals.

The present invention provides a method for the exhaust dyeing oftextiles using a select class of dyes at significantly lower levels ofelectrolyte in the dye bath with the attendant reduction in rawmaterials costs, reduced chemical discharge to the environment andreduced waste water treatment costs. An additional advantage is that theprocess of the invention unexpectedly gives a higher dyeing efficiencyas evidenced by the achievement of higher dye build up values.

The advantages and unexpected properties of the dyes of this inventionare shown in the following comparison of the invention with commercialpdor art dioxazine dyes.

Cotton test fabrics were dyed by the exhaust method at a 2% dye leveland a liquid ratio of 10 to 1. The dyeing was conducted at 60° C. and inaddition to the salt component, the dye bath contained 15% by weightsoda ash and 1% by weight sodium hydroxide. The test specimens were dyedunder substantially the same conditions and the color yield measured ona computer assisted spectrophotonomer with the color yield beingmeasured in color density units (CDU).

    ______________________________________                                        EXHAUST DYEING                                                                (Color Yield vs Soft Concentration)                                           ______________________________________                                        Example 1 (The Invention)                                                     Salt g/l  100     50       30    20     10                                    CDU       1.067   1.044    1.127 1.094  1.11                                  Rel. CDU %                                                                              100     97.8     105.6 102.5  104.6                                 C.I. Reactive Blue 198 (Prior Art)                                            Salt g/l  100     50       30    20     10                                    CDU       0.837   0.795    0.649 0.575  0.481                                 Rel. CDU %                                                                              100     90.7     77.5  68.7   57.5                                  C.I. Reactive Blue 204 (Prior Art)                                            Salt g/l  100     50       30    20     10                                    CDU       1.638   1.486    1.376 1.319  1.06                                  Rel. CDU %                                                                              100     90.7     84    80.5   64.7                                  ______________________________________                                    

The invention may be embodied in other specific forms without departingfrom the spidt or essential characteristics thereof. Through thisspecification and the appended claims, a given chemical name or formulais intended to encompass all isomers of said name or formula where suchisomers exist. The present embodiments are therefore to be considered inall respects as illustrative and not restrictive, the scope of theinvention being indicated by the appended claims rather than by theforegoing description; and all changes which come within the meaning andequivalency of the claims are therefore intended to be embraced therein.

We claim:
 1. A dyestuff of the formula: ##STR61## wherein T isindependently selected from Cl and Br; Q is: ##STR62## K is SO₃ H; n isindependently selected from 0 or 1;R₂ selected from hydrogen or C₁ to C₄alkyl; R₄ is selected from H, Cl, Br, C₁ to C₄ alkyl, or C₁ to C₄alkoxy; D is selected from a covalent bond or C₁ to C₆ alkylene whichmay be interrupted by a hetero atom selected from O, N or S; and Y¹ isselected from vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-halogenethylor β-phosphatoethyl.
 2. A dye according to claim 1 having the followingformula: ##STR63##
 3. A dye according to claim 1 having the followingformula: ##STR64##
 4. A dye according to claim 1 having the followingformula: ##STR65##